Catalytic conversion of saturated hydrocarbons to unsaturated products by oxidation in the presence of a halogen

ABSTRACT

The instant application is related to a process for the oxidation of saturated hydrocarbons and substituted saturated hydrocarbons in a vapor phase reaction over an antimonycontaining oxidation catalyst in which the hydrocarbon in the presence of a minor quantity of an inorganic or organic halide, hydrogen chloride, hydrogen bromide or hydrogen iodide or of a halogen other than fluorine, is reacted with (a) oxygen, to form unsaturated aldehydes and acids or (b) oxygen and ammonia, to form unsaturated nitriles.

United States Patent Grasselli et a1. 4 Aug. 22, 1972 CATALYTIC CONVERSION OF 3,468,958 9/1969 Callahan ..260/533 N SATURATED HYDROCARBONS To 3,506,708 8/ 1970 Ball et a1 ..260/533 N UNSATURATEI) PRODUC BY 3,542,842 11/1970 grasselli et al. ..260/533 N OX 3,544,616 12/1970 rasselli et al. ..260/533 N IDATION IN THE PRESENCE OF A 3,551,470 12/1970 Sharo et a1 ..260/533 N HALOGEN Inventors: Robert K. Grasselli, Garfield Heights; Robert C. Miller, Northfield, both of Ohio Assignee: The Standard Oil Company, Cleveland, Ohio Filed: June 1, 1970 Appl. No.: 42,460

Related U.S. Application Data Continuation-in-part of Ser, No. 739,166, June 24, 1968.

U.S. C1. ..260/533 N, 260/604 R, 260/599, 260/524 R Int. Cl. ..C07c 51/20, C07c 45/02 Field of Search ..260/533 N, 604 R References Cited UNlTED STATES PATENTS 2/1969 Callahan eta1. ..2 60/533 N Primary ExaminerLorraine A. Weinberger Assistant ExaminerRichard D. Kelly Attorney-John F. Jones and Sherman J. Kemmer [57] ABSTRACT 5 Claims, No Drawings CATALYTIC CONVERSION OF SATURATED HYDROCARBONS TO UNSATURATED PRODUCTS BY OXIDATION IN THE PRESENCE OF A HALOGEN CROSS REFERENCES TO RELATED APPLICATIONS This is a continuation-in-part of our co-pending US. Pat. application Ser. No. 739,166 filed June 24, 1968.

BACKGROUND OF THE INVENTION Unsaturated aldehydes such as acrolein, methacrolein, cinnamaldehyde and atropaldehyde, unsaturated acids such as acrylic acid, methacrylic acid, cinnamic acid, a-phenyl acrylic acid, and the like are highly desirable compounds having particular use as specialty industrial chemicals and as monomers and comonomers in a variety of commercial polymers. Un saturated nitriles such as acrylonitrile, methacrylonitrile, cinnamonitrile, atroponitrile and the like are similarly useful chemicals used in the manufacture of fabrics, insecticides, herbicides and plastics. The aforementioned unsaturated compounds are usually manufactured from monoolefinically unsaturated compounds such as propylene, isobutylene, isoamylene, a-methyl styrene, B-methyl styrene and the like which are considerably more expensive raw materials than more readily availably saturated and substituted saturated hydrocarbons. To date, commercial manufacture of the desired unsaturated compounds has been most successfully achieved by the vapor phase oxidation or ammoxidation of an olefin or an olefinically unsaturated alkyl aromatic.

Much time has been spent on various methods of converting the cheaper saturated compounds into the desired more valuable unsaturated nitriles, aldehydes and acids in a single step catalytic reaction. Particularly noteworthy is the fact that considerable effort has been expended to effect the desired oxidation of saturated hydrocarbons without breaking off one or more carbon atoms. This effort has met with a conspicuous lack of success and served to focus on the gap in this technolo- I gy. The instant invention aims to fill that gap.

US. Pat. No. 3,365,482 teaches a process for the ammoxidation of saturated hydrocarbons and as background, lists a number of references which teach the ammoxidation of olefinically unsaturated hydrocarbons. Also included is a summary of the difficulties inherent in a process for the ammoxidation of saturated hydrocarbons, which difficulties no one will gainsay.

In US. Pat. No. 3,293,290 a process is disclosed for the manufacture of unsaturated aldehydes and acids from either paraffins or monoolefins in which a gaseous mixture of hydrocarbons and oxygen is catalytically converted into the desired products in the presence of hydrogen bromide or hydrogen iodide as a promoter.

products are reproduced from said reference under the heading Desirability of Chloride Promoter in the Examples section of the instant application.

Another halide-promoted catalytic reaction is the subject of US. Pat. No. 3,293,292 wherein liquid normal butane is converted to acetic acid in the presence of a cobalt salt which is soluble in the liquid medium in which the oxidation reaction takes place. It will be noted that, unlike the reactions disclosed in US. Pat. No. 3,293,290 and the instant invention, the liquid phase reaction involves converting a lower alkane to the saturated acid rather than the unsaturated acids and aldehydes.

In the instant invention, applicants have discovered that saturated hydrocarbons and substituted saturated hydrocarbons having from three to 12 carbon atoms.

per molecule, and preferably from three to nine carbon atoms per molecule, may be readily oxidized or ammoxidized by the instant vapor phase catalytic reaction utilizing an antimony-containing oxidation catalyst provided that a minor quantity of an inorganic or organic halide, a halogen or a halogen acid, as specified hereinafter, is incorporated with the feed. Fluorine and compounds of fluorine are excluded from the scope of the instant invention.

SUMMARY It is an object of the instant invention to provide a commercial vapor-phase oxidation process for the conversion of inexpensive alkane and aryl-substituted alkane hydrocarbon feedstocks into more valuable unan alkane or aryl-substituted alkane feed having from three to nine carbon atoms in the presence of halogens other than fluorine, halogen acids other than hydrogen fluorides, lower alkyl halides other than fluorides, and

ammonium halides, other than anunonium fluoride, in the vapor state, in conjunction with a molecular oxygen-containing gas over an antimony-containing solid oxidation catalyst to form unsaturated nitriles, aldehydes and acids.

DESCRIPTION OF THE PREFERRED EMBODIMENT It has been found that when small quantities of chlorine, bromine and iodine or certain halides are included in saturated hydrocarbon feed which is passed over the antimony-containing oxidation catalysts disclosed herein, said catalysts show an unexpected and surprisingly high activity toward the otherwise relatively inert paraffinic feed materials. The instant reaction is unique in that the halogen or halide acts as a promoter with known oxidation catalysts.

Compounds which may be oxidized or ammoxidized by the instant process have the structure wherein R R and R may be hydrogen, an alkyl or an aryl group, or a substituted alkyl group wherein the substitution is an aryl group, provided said compounds contain at least three carbon atoms. The alkyl groups have from one to eight carbon atoms per molecule (as, for example, methyl, ethyl, isobutyl and hexyl) and preferably from one to four. Most preferred of the aryl groups is the phenyl group. Most preferred reactions are (a) the ammoxidation of propane to acrylonitrile, isobutane to methacrylonitrile, isopropyl benzene to atroponitrile and n-propyl benzene to cinnarnonitrile and (b) the oxidation of propane, butane, isobutane, pentane, isopentane, hexane, isohexane, n-propyl benzene and cumene, to form unsaturated aldehydes such as acrolein, methacrolein, crotonaldehyde, 'yethyl acrolein, B-ethyl crotonaldehyde, 2-henenal, yamylacrolein, cinnamaldehyde and atropaldehyde, and unsaturated acids such as acrylic, vinyl acetic, crotonic, methacrylic, isopropyl acrylic, and cinnamic acid.

The preferred hydrocarbons are the low boiling alkanes having between three and six carbons. More preferred compounds are propane, isobutane, pentane and isopentane.

Generally, in the production of unsaturated aldehydes by the instant process, some unsaturated acids, olefins and other by-products of reaction will be formed; in the manufacture of unsaturated nitriles and acids, some unsaturated aldehydes, olefmic and saturated by-products may also be formed which may be recycled for further conversion to the desired unsaturated acids. When an inorganic halide such as ammonium chloride is used in a process for making predominantly the unsaturated aldehydes and carboxylic acids, some unsaturated nitrile will also be formed due to the liberation of an active nitrogen-containing species in the reaction. Similarly the use of a lower alkyl halide would yield, in addition to the desired unsaturated a1- dehydes and carboxylic acids, the unsaturated aldehyde or carboxylic acid formed from the alkyl group introduced. Thus propane oxidized in the presence of isobutyl chloride will yield, in addition to acrolein and acrylic acid, some methacrolein and methacrylic acid. It is possible to use aromatic halide compounds in which the alkyl group on the aromatic nucleus contains a halogen substitution. Such compounds give rise to the formation of unsaturated aldehydes and acids containing the same number of carbon atoms as the halogencontaining compound. Thus isobutane oxidized in the presence of B-chloro-isopropyl benzene will yield in addition to methacrolein and methacrylic acid, some cinnamaldehyde and cinnamic acid. In general, the high cost of halogen-containing alkyl-substituted aromatic compounds will preclude their usage in most applications.

Catalysts that are particularly useful in the instant invention are the unpromoted catalysts disclosed in US. Pat. Nos. 3,197,419; 3,198,750; 3,264,225; 3,200,081; 3,152,170; 3,198,751; 3,244,642; 3,258,432 and 3,200,084; and the promoted oxidation catalysts disclosed in U.S. Pat. Nos. 3,326,819; 3,338,952 and 3,269,957. It is known that catalysts in the above-identified patents are quite illsuited to the oxidation of paraffms, being substantially inert, though they are very effective catalysts for the conversions of monoolefms to the corresponding unsaturated aldehydes and acids. It is therefore all the more surprising that these catalysts, which may be prepared by any of the means described in the aboveidentified patents, and which may be disposed on any suitable catalyst support also as specified in the aboveidentified issued patents, should exhibit such a surprisingly high activity towards a paraffinic feed as long as the feed included a halogen other than fluorine or a halogen acid other than hydrogen fluoride, or ammoni um halide other than ammonium fluoride, or a lower alkyl halide, preferably those having from three to six carbon atoms. Other inorganic and organic halides may be used but the relatively high cost of said halides is not offset by a superior yield of desirable products. Generally, the halogen or the halogen-containing compound should be added so as to be in the vapor phase in the feed, when the feed is passed over the oxidation catalyst. A relatively small quantity of halogen or halogen-containing compound should be sufficient, generally in a concentration in the range from about 0.001 to about 25 volume percent (calculated as molecular halogen) of the hydrocarbon feed; the more preferred range of halogen in the feed is from about 0.01 to about 10 volume percent (calculated as molecular halogen) of the hydrocarbon feed.

Oxygen for the oxidation reaction may be supplied either as elemental oxygen, air or in any molecular oxygen-containing gas where the components other than oxygen do not interfere with the production of the desired unsaturated oxidation products. In general, from about 0.5 to about 5 moles, but preferably about 1 mole of oxygen per mole of hydrocarbon feed is included in the mixture conducted to the reactors. If desired, oxygen, as well as diluents such as steam and inert gases, may be introduced separately into predetermined parts of the reaction zone.

Ammonia for the conversion of saturated hydrocarbons to unsaturated nitriles may be supplied either as a liquid to the reactor or more preferably, as a preheated gas. In general about 1 mole of ammonia per mole of hydrocarbon feed is included in the mixture conducted to the reactors. Either more or less ammonia may be used, but there is no advantage in using much less or much more than the theoretically indicated amount.

Any reactor, whether fluid-bed or fixed-bed, may be used in the instant process. Reactors suitable for the exothermic process of the instant invention will usually be equipped with heat exchange coils, quenching means, cyclones and the like.

The contact time for the reaction will depend upon various factors, among them the type of catalyst used, its surface area and physical and chemical characteristics, the products desired, whether they be the unsaturated acids or the aldehydes, and the heat of reaction for the particular products desired to be manufactured. In general contact times are short, ranging from about 0.1 to 20 seconds, The contact time, sometimes referred to as the apparent contact time, is determined from the apparent volume of the catalyst and the mass flow of the gases through the reactor.

The temperature is maintained in the reaction zone by preheating the feed to a suitable temperature before it enters the reactor. The exothermic heat of oxidation, once the reaction is initiated, will often suffice to maintain the reaction, and excess heat of reaction is removed by the injection of water sprays and by suitable heat transfer devices with which the reactor is equipped.

In general, when operating at pressures near atmospheric, i.e., to 100 psig, temperatures in the range of 500t0 1,100 F may be advantageously employed. However, the process may be conducted at other pressures, and in the case where superatmospheric pressures, i.e., above 100 psig are employed somewhat lower temperatures are possible. In the case where this process is employed to convert propane to acrolein, a temperature range of 850to l,0O0 F has been found to be optimum at about atmospheric pressure. While pressures other than atmospheric may be employed, it is generally preferred to operate at ,or near atmospheric pressure, since the reaction proceeds well at such pressures and the use of expensive, high-pressure equipment is avoided.

Reaction products from the reactor emanate as a hot gaseous stream which may be first heat exchanged with incoming feed gases, and then quenched by a suitable liquid, water generally being used. Suitable inhibitors are added to the aqueous solution to prevent polymerization of reaction products and to facilitate their separation and recovery in subsequent operations.

The following examples will serve to illustrate our invention and present typical results which were obtained. All parts referred to are parts by weight, and all ratios are molar ratios, unless otherwise specifically designated.

All conversions are given as Per Pass Percent Conversion and defined as:

Moles of unsaturated product formed per pass Moles of saturated hydrocarbon fed per pass Test 1 2 Unsaturated Products (percent yields) Acrolein 50 40 Acrylic Acid 1 l l l Promoter (Vol. None 0.2 HCI Overall Conversion 9.7 7.6

Thus 9.7 mols of 100 mols propylene are converted without a promoter while only 7.6 mols are converted with an HCI promoter. It is apparent that, when one uses the same catalyst, not only is conversion of the feed higher with no promoter at all, but the net make of desirable unsaturated products is also better. Test 1 shows that 100 mols of hydrocarbon (propylene) passed over the unpromoted catalyst result in a net make of 4.85 mols of acrolein and 1.067 mols of acrylic acid; but over the HCI promoted catalyst, Test 2 shows a net make of only 3.04 volumes of acrolein and 0.836

Test 6 8 l0 unsaturated products (percent yields) Acrolein Acrylic Acid Overall Conversion Acrolein,

Net Make Acrylic Acid,

Net Make ll.l 8.0 7.3 13.5

*calculated Clearly these data would suggest that halide promotion of oxidation catalysts, particularly of the iron and bismuth salts of phosphomolybdic acid is of little more than academic curiosity.

EXAMPLE 1 Quartz (C.P.) was crushed and screened; the particles within the range from 20-35 mesh Tyler Screens) were loaded into a reactor of approximately ml. capacity. When the reactor attained the desired temperature, the gas feed was metered into it by Rotameters, the individual components of the gaseous feed being mixed in a manifold immediately prior to entering the reactor. A run without the halide promoter preceded one using the halide promoter which was introduced into the manifold in a gaseous state. Water was usually added to the feed as liquid, to facilitate temperature control, by a Sigmarnotor pump through capillary tubing which could be preheated if desired, prior to entering the manifold.

TABLE I Per pass percent conversion to Halide Reactor Contact Material promotemp., Feed, i-C4/ time Aldein reactor tion C. air/Hzg/HCI (secs) Olefins hydes Crushed quartz.- None 600 1/11/5/0 3. 5 G. 0 I. 6 Do... HCl 600 1/11/6/0.25 3.5 40.6 6.4

EXAMPLES 2-4 TABLE 11 Successive examples were run with other catalysts in a manner similar to that described above. Each catalyst used is identified hereinbelow with an alphabetical code corresponding to footnotes that refer to the details of their preparation as found in specific references. All catalysts were supported on silica.

Feed ratio l-Cr/ Reactor Contact Per pass percent conversion to Catalyst in N Hg/Alr/Oz/HzO temp., time acry1o- Acrylo- Example reactor HCl 0. (secs) nltrlle nitrlle 2 USbMOim 1/1. 5/10/1/5/0 550 3. 2 3. 9 2. 9 USbuOim 1/1. 6/10/1/5/0. 25 525 3. 3 11. 3 8. 2

4 USbflOim 1/1. 5/10/1/5/0. 25 650 3. 2 10. 14.

EXAMPLES 5-14 An antimony-iron catalyst was prepared as described in Example 2 of US. Pat. No. 3,341,471. The heattreated catalyst was loaded into a reactor with about 100 ml. catalyst capacity. The components of the gas feed were metered by Rotameters and mixed in a manifold immediately prior to entering the reactor when the desired reactor temperature was attained. A hydrocarbon mixture in the volumetric ratios indicated hereinbelow in Table 111 was fed to the reactor and the effluent analyzed for the reaction products. Water was added to the feed as liquid to facilitate temperature control, as in the previous Example 1. In some examples the hydrocarbon feed was passed over the catalyst, first, without any halogen or halide promoter and the reaction products were analyzed. Immediately thereafter a run was made under identical conditions, except that a halide promoter (hydrogen chloride gas) was used.

TABLE ill The containing catalysts described above gave comparable results with hydrogen bromide and iodide; ammonium halides and lower alkyl halogen-substituted hydrocarbons disclosed herein were also effective promoters.

Other antimony-containing catalysts which contained bismuth, platinum, boron, silver, cobalt, nickel, lead, arsenic, tungsten, phosphorus, aluminum, calcium and cesium gave similar results when a saturated hydrocarbon was ammoxidized in the presence of hydrogen chloride, bromide or iodide; chlorine, bromine, or iodine; ammonium chloride, bromide or iodide; and lower alkyl halides containing from three to six carbon atoms.

EXAMPLES 15-23 The runs set forth in Table IV hereinbelow were performed in a manner similar to those set forth in Table 111 above, except that no ammonia was introduced into Per pass percent conversion to Feed ratio, i-C Reactor Contact Metha- NHflalr/Oz/HzO/ temp., time crylo- Acrylolax-ample Catalyst 1n reactor H01 0 (secs) nltrilo nitrile 5... Antiniony-=- iron oxides 1/2/11/0/5/0 600 3.15 do 1/2/11/0/5/0. 25 600 3. 15 13. 5 1. 6 o Ant monythorium oxides 1/ 1. 5/11/0/5/0. 25 550 3. 5 16. 7 14. 3 7 Ant monymanganese oxides 1/1. 11/0/5 0. 25 550 3. 5 15. 9 11. 2

Antimonytin oxides 1/1. 5/11/0/5/0. 25 550 3. 5 20. 3 12. 2 9 Iron-promoted antimony-uranium oxides, FerUSbuOrrz. 1. 5/1 1/5/() 520 4.0 1.8 0 do 7 1/1. 5/10/1/5/0. 25 520 4. 0 35. 9 18. 8 10.... Copper-promoted BHUIHOIIYUIHHIDITI oxides, Cu,3USb4.eO1: a 1/1. 5/10/1/5/0. 25 540 3. 9 14. 1 13. 6 11 Copper and bismuth: promoted antimony-uranium oxides, Cu, 5Bi,15USb4.u

01:.7- I l/l. 5/10/1/5/0. 25 520 3. 17. 3 13. 3 12 Cobalt-pron'ioted antimony-uranium oxides, Co.1USb4,a0n 5 1/1. 5/10/1/5/0. 25 540 3.90 15. 4 9. 7 Nickel-promoted antimony uranium oxides, N1.5USb4 BO13,8 1/1. 5/10/1/5/0. 25 560 3.85 11. 3 13.0 14 Magnesium-promoted antimony-uranium oxides, 1\Ig,2Usb|,flOl3,6 1/1. 5/10/1/5/0. 25 560 3.9 12. 5 10. 6

* See U.S. Patent No. 3,341,471; See U. S. Patent No. 3,328,315.

TABLE IV Per pass percent conversion to- Reactor Contact Feed ratio, Temp., time Meth- Example Catalyst; in reactor i-C,/air/Oz/II20/HC1 C (5003.) acrolein Acrolein 15 Uranium-antimony oxides USb4 flOl3,2 1/8. 2. 6/6/0 550 3. 2 0.3 0. 6 16 do 1/8. 6/2. 5/5/0. 25 550 3. 2 17. 2 23. 1 17 Iron-antimony oxides, FOSbBJOlfl 1/11/0/5/0- 25 600 3. 4 16. 4 5. 4 18 Antimony-thorium oxides /0 5 550 3. 2 11.1 9.3 19 Antimony-manganese oxides 1/11/0/5/0 25 500 3.4 21.0 11.6 20 Antimony-tin oxides 25 500 3. 4 19. 8 8.7 21 Iron-promoted antimony-uranium oxides, FeiUSbMOiM /0/5/0- 25 500 3.4 31. 2 15. 3

C /air/O2H 0/HCl 22 Iron-promoted antimony-uranium oxides, F04 USbMOnn /10/1/5/0. 25 500 3. 4 20. 9

Ca/air/Oe/HzO/HBr 23 Iron-promoted antimony-uranium oxides, FGJ Sbi-uOiim 1/10/1/5/0. 25 470 3.5 29. 8

the reactor. Thus the unsaturated aldehydes and acids were formed. In the examples immediately following, only the amount of unsaturated aldehydes formed are shown as the unsaturated carboxylic acids formed were minor quantities, the conditions of reaction having been adjusted to favor the formation of the unsaturated aldehydes. All catalysts were supported on silica and prepared as before.

Other antimony-containing catalysts which contained bismuth, platinum, boron, silver, cobalt, nickel, lead arsenic, tungsten, phosphorus, aluminum, calcium, tin, vanadium, cerium and cesium gave similar results when a saturated hydrocarbon was oxidized in the presence of hydrogen chloride, bromide or iodide; chlorine, bromine or iodine; ammonium chloride, bromide or iodide; and lower alkyl halides containing from three to six carbon atoms.

EXAMPLES 24-26 The following runs were made using a copper and magnesium promoted antimony-uranium catalyst, prepared as disclosed in US. Pat. No. 3,328,315, to demonstrate that with certain catalysts, increased reactor temperatures, with a halide promoter, will give increased conversions of the saturated hydrocarbon to desired unsaturated nitriles.

EXAMPLES 27-28 Halide promotion of certain promoted antimonycontaining oxidation catalysts exhibits a sensitivity to temperature, in that arelatively small change of reactor temperature coupled with a change in the ratio of the feed components can form more of one product Antimony-containing oxidation catalysts were used for the arnmoxidation of saturated hydrocarbons other than isobutane. The procedure for carrying out these runs was similar to that described in Examples 3-8 hereinabove. Some of the hydrocarbon feeds ammoxidized over particular catalysts gave unsaturated nitrile products described in the Table immediately below.

TABLE VII Per pass percent Reactor Contact conversion to temp., time unsaturated Example Catalyst in reactor Feed components, ratio in feed 0. (secs.) nitriles C /Nll lairlozlllzO/HCI Acrylonitrile 21L. lmn-promotml nntiluor\y-urnniulnoxides, FlJUSbLUOlLIJl 1 Hui-M n 600 3. 85 i i 3n Anlimony-imnoxides, Fer b mhru" l/l.5/l0/l/5/().25 500 3.15 11.3 "i'iitiaofiieiit 32 Iron-promoted antimony-uranium oxides, Fc.rUSb4.e0ia .4 umene/NHa/uir/Or/HaO/HCl 480 2. 0 3 73 TABLE V Catalyst in Reactor: Cu IVIg USb O feed ratio (i-CJNH IAir/OJH OIHCI): 1/ 1 .5/ 10/ 1/ 5/025 Per Pass Percent Conversion to EXAMPLES 33-38 The examples hereinbelow demonstrate that various inorganic halides, certain organic halides, particularly the lower alkyl halides having'from two to five carbon 523 :1223; gf z mf 22m mgglfg atoms, in addition to the halogens and the halogen c (secs Nitriles acids, except that the halogen should not be fluorine,

50 may be used in the instant invention. g; 22 :1 2-3 33 In general, the use of bromides and iodides will per- 26 560 3 g5 174 15,7 323 mrt the use of lower reaction temperatures and contact times.

TABLE VIII Catalyst in reactor: Iron-promoted antimony-uranium oxides Fe.iUSb4.oOi3.4

Per pass percent Conversion to- Reactor Contact Metha- Temg. time crylonr- Acrylom- Example Feed components, ratio in feed (sccs.) tri tn 33 "{i-C4/NH3 alr/OfllhO/HBr 450 4. 5 38. 8 5.1

1/1.5/10/1/5/0.25 34 {i-C4/NH3/8if/OzlfIzO/HI. 510 4. 1 40. s 4. 4

1 1.5 10/1 .25 35 gi-CilNHi/Airlor/lIrO/NILC1.. 640 4. 0 25. 7 s. s

1 1.5/10/1 5 0.25 34' .{l-Cr/NlhlalrloglllgO/n-propylbromide. I 450 4.5 32.3 21.7

1/1.5 w 1 5 0.25 l 37. (U.1/N|I: Itllll()2/llyfllulllyl chlnrlrle. mm 1.0 (l

u 1.5 m 1 5 u.-. r,.... I I 3a.. C /Nlh/ulr/(h/llrU/lll$r 4!) 4.0. $5.7

ll/l.5/10/1/5/.025

We claim:

1. A process for the preparation of monoolefinically unsaturated aldehydes and carboxylic acids containing from three to nine carbon atoms consisting essentially of reacting hydrocarbon selected from the group consisting of propane, butane, isobutane, pentane, isopentane, hexane, isohexane, n-propyl benzene and cumene with a molecular oxygen-containing gas in the presence of a halogen or halogen-substituted compound selected from the group consisting of a halogen selected from the group consisting of chlorine, bromine and iodine, a member selected from the group consisting of hydrogen chloride, hydrogen bromide and hydrogen iodide, a lower alkyl chloride, bromide or iodide, and an ammonium halide selected from the group consisting of ammonium chloride, ammonium bromide, and ammonium iodide over a catalyst consisting essentially of antimony oxide in combination with at least one other polyvalent metal oxide, selected from the group consisting of uranium, iron, thorium, manganese and tin, and optionally at least one other polyvalent metal oxide selected from the group consisting of copper, bismuth, nickel, cobalt, magnesium and zinc said antimony being present on a molar basis as the major polyvalent metal component in a pressure range of from about 7 pounds per square inch absolute to about 300 pounds per square inch absolute, at a temperature of from about 250 C to about 800 C, and recovering the monoolefinically unsaturated aldehydes and carboxylic acids formed.

2. The process of claim 1 wherein the amount of halogen in said halogen or halogen-substituted compound is present in a concentration from about 0.001 to about 25 mole percent of the saturated hydrocarbon introduced into the reaction zone.

3. The process of claim 1 wherein the amount of said halogen or the amount of molecular halogen in said halogen-substituted compound is present in the range from 0.05 to 15 mole percent of the saturated hydrocarbon introduced into the reaction zone.

4. The process of claim 3 wherein said molecular oxygen containing gas is air.

5. The process of claim 4 wherein the molar ratioof said saturated hydrocarbon to air is in the range from 1:5 to 1:200. 

2. The process of claim 1 wherein the amount of halogen in said halogen or halogen-substituted compound is present in a concentration from about 0.001 to about 25 mole percent of the saturated hydrocarbon introduced into the reaction zone.
 3. The process of claim 1 wherein the amount of said halogen or the amount of molecular halogen in said halogen-substituted compound is present in the range from 0.05 to 15 mole percent of the saturated hydrocarbon introduced into the reaction zone.
 4. The process of claim 3 wherein said molecular oxygen containing gas is air.
 5. The process of claim 4 wherein the molar ratio of said saturated hydrocarbon to air is in the range from 1:5 to 1:200. 